Abstract
A family of CoFe Prussian blue analogues C x Co 4[Fe(CN) 6] (8+ x/3) □ (4– x )3 ( x = amount of alkali cation inserted per conventional cell, C = Na, K, Rb, Cs; □ = [Fe(CN) 6] vacancy) have been synthesized and characterized. Their photomagnetic properties have been investigated by magnetic measurements before and after irradiation and X-ray diffraction under continuous irradiation. We show that the photo-induced magnetism depends on several parameters: ( i) the amount of Co III–Fe II diamagnetic excitable pairs per cell; ( ii) the amount of [Fe(CN) 6] vacancies, and ( iii) the amount and nature of the alkali cations per cell. We evidence a discontinuity in the properties' change when the amount of alkali cation x varies, around x = 1. For x < 1, there is an excitation of diluted Co III–Fe II diamagnetic pairs in a phase mainly composed of magnetic Co II–Fe III entities within the same structural phase through a second-order continuous transformation. For x ≥ 1, the formation of domains mainly composed of Co II–Fe III* metastable magnetic pairs in a phase mainly composed of Co III–Fe II diamagnetic ones through a first-order discontinuous transition is observed. The study points out that sodium derivatives are more efficient than the others. Among them, Na 1Co 4[Fe(CN) 6] 3□ 1 is predicted to be the most efficient one. To cite this article: A. Bleuzen et al., C. R. Chimie 6 (2003) .
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